A subs trate-independent method has been devised for ring formation at solid surfaces. This entails the aminolysis reaction of allylamine with maleic anhydride pulsed plasma polymer films to yield terminal alkene groups at the surface. Subsequent exposure to 1,3-cyclohexadiene leads to a Diels-Alder type (4 + 2) cycloaddition reaction to give a mixture of endo- and exo-bicyclo[2.2.2]oct-2-ene rings.